Manufacture of alkyl acid salts



F U'NI T a mmmrtnt on;

aosssoi CID 1 N Drawing. Applic My inventionrelates to the preparationjof alkyl H u artificially-introduced chemically-combined ,oxyy,

a gen, such as the mixture obtained by partial ox-,

u idation of petroleum fractions with air-or agas containing oxygen; with sulphuric acid or,equiv-,] talent inorganic acids :such as those having three orrnore replaceable hydrogen atoms,as well as the c cdrresponding pyro" acids andalso acids other l0 thansulphuricacidjhavingalower oxygen content 7 than those first named, such as the tous acids,

including? phosphorous acid, arsenious acid, etc. i I intendlto include all such equivalent acids such as boric acidphosphorics acid, arsenic acid, etc" 15 In my previous PatentNo. 1,753,516 of.April8,, l930, lhave described sui ho aanemynartiai oxidation productsflof hydrocarbon such as pew troleum fractions, and in my copendingapplications Ser.-No.688,862,;flled SeptemberQ, 1933 and,

Ser. No; 759,239, filed December .26, {1934, Ihave, udisclosedsuch treatments. ,1 1 i In further investigation and researchyalong theselineal have discovered that it is of special advantage in such processes, ,toincrease the per centage of unsaturateds inwthe partial oxidation mixture: .This oxidation mixture when produced by vapor phase partial oxidation process contains, each invarying weights, such bodiesfas 911-; ,cohols, alkyl aldehydespaldehydes, lactones, ker tones, esters, ethers andoxygenated,organicacids, including some unsaturated compounds as there always been somepracking incidental to my process onjaccountbf the temperatureused which normally, runsw'above 250" C. and under 500? C.

Inorder to in'crease the unsaturated contentcf such a condensed partial oxidation product, I have devisedtwo different species of ,processunder the genus of -increasing the percentage of unsaturateds therein. One of f such :methods consists oxidation process-in the normal manner-and then 11 passing theexit gas with its content of the vaporized mixture recited abovetandproduced by partial oxidation; through a cracking apparatus after the partial'oxidation :p'rocessyhas been carried out. This cracking preferably contains or *yconsists bf acatalystto assisttin the cracking operation, this, for instance, being nickel, as by H passing theexit mixture through a heated nickel 3 y 50 tube maintained at a cracking temperature for example, 550 C. u i

P The other species con sists essentially in carrying out my vapor phase partial oxidation process itself at a higher temperature, thantheretofore, especially a temperature within the red heat SerialNo. 16,013 7 (01. 2603-9912) acid'* esters -flby treating a hydrocarbonlhaving primarily in carrying out my vapor phase partial i not April 12, 1935,

j range, such for exampleas 520 C., andpreventing ignition of and wasting of the charge by actual complete combustion, preferablyby adding water onsteain Also, in such case, I preferably employ a catalyst ofthe type which is not volatileat the 5 temperature used, such for exampleas vanadium pentoxide. W I c I will now describe these two difierentspecies more in detail and give examples in each case. I. In my vapor phase catalytic oxidation, the 10 product mixture contains as above shown, alcohols, aldehydes ketones and oxygenated acids. While carboxylic acids are obj'ectionableif present inlarge amounts because of the calcium in solubility thereof, my present proceduretendsto eliminate, the carboxylic groups, still leaving sulphatable molecules. Under these speciesQin preparing the material for sulphat i -sulphonatlng, I preferably increase the contentofunsaturateds j by fcracking" the partial oxidation productmixtu're, preferably while in the'vapcr phase. This M generaLprccess of cracking such aproductmixture is disclosed in myPatent No. 1,587,796 of 1 August 31, 1926, which,however, contains no clisclosure as to the advantages and peculiar adaptability of such a cracked product for' producing alkyl acidsaltsp I have nowfound that such a cracking processc applied to a partial oxidation product reduces the gaslosses and formation oi} side products,

and hence, is advantageous we; theoxidation of previously cracked material and also is of ad-' vantageinithat i'orthe manufacture ofdetergents, I can separate out remove thelighter portionof theproduct, thus using only the heavier portion, preferably above Cs or Caand essentially from C12 to C24 for,sulphating sulphonating, thus obtaining, alkyl acid salts which are particularly and peculiarly adapted for detergent use.

By cracking the partial oxidation product, I 40 controlv toa better extent the average molecular weight of the sulphatable product, since the opening up, of the molecules for sulphation is acv complished by breaking offragments or endpor:

tions of theoxidizedportions,"such as carbon monoxideand carbon dioxide, rather than by the scission or breaking cfthe molecules into two nearly, equal parts, whichoccurs in the case of i the plain cracking of straight hydrocarbons. This clipping orcutting off of a few carbon atoms in the case of thermal decomposition of the par tial oxidation productresults in making the mixture easier and better to sulphate, while the majority of the mixture will thus come within the range of the best detergents, namely C1: to C 4.

25 lyst for about two seconds;

out by fractional distillation. or otherwise, to give the desired or best carbon range in-thematerial which is subjected to suiphating-suiphonating or i its equivalent.

trample 1.The material subjected to thermal decomposition was the partially oxidized product obtained, by my vapor phase catalytic method wing a molybdenum oxide catalyst and a proper l temperature of air containing free oxygen applied to a Coastal" lubricating oil"(300 via). The cracking apparatus consisted of, anickel tube 30 inches long and 1% inch inside diameter, and the catalytic material consisting of 20% nickel and .20 80% asbestos.

The quantity of thiscatalytic material was such that the vapor exit mixture from the, oxidation apparatus which entered it at the rate 01' 200 cc. per hour wasin contact with the cata- A temperature of aboutf550 C..'was maintained inthe' nickel tube byexternal heating.fconsiderable quantities of gas 1 were formed and from 75ii'jcc. of oxidation mixture fed, 565 cc. of "liquid cracked product was r 0 obtained giving a volume percentage yield of 62%. The specific gravity of the original oxidal tion;mixture,was .939, .whi1etha t of thecracked "product wasslightly higher, about .957.

T Whenthe cracked product thus obtained was 85 sulphated-sulphonated by the addition of sulphuric acid, asset forth ior example in my Patent No. 1,753,516, it gave a 65% contraction for the cracked product as against 48% contraction for the original oxidation mixture. Sulphate-sul- 40 phon'ate soaps made from the cracked product showed better detergentproperties in hard water than similarproducts made 'from' the original "oxidation 1 .Of course, other catalysts may be'used than '45 above named, such for example, as magnesium oxide; .or'noca'talyst at all maybe in the cracking step." V

other speciesfherein' set forth when t preparing for the m'akingof alkyl acid salts, I 50 increase the percentage of ,unsaturateds by cartying it my vapor oxidation process at a higherten peraturethan otherwise employed, at a temperaturewithin' a red fheat. a temperature increases the gasiosses, but

as excessive loss is prevented by feedin ,Water or 0131a diluent, whichprevents the. ignition and complete continuous combustion.

again to ulphating-sulphonating in the broad senseherein used, it is desirable for w s purpose to obtain my product with a light percentage ot unsaturatedhydrocarbonsand a .of .molecules' carrying Q carboxylicgroups, since the latter, on saponification to form sodium soaps, will form insoluble soaps of calcium, iron' oraiuminum, if used in waters such solublelsalts. The unsaturated hydrocarbons and. alcoholsreact withsulphuric acid to make alkyl acid esters or sulphuric acid,-

the soaps of which have the desired properties in hard water. Other oxidizedbodies than the .carbonlic acids, as i'or'ex'ample, the ketones and aldehydes, i'orm sulphonates during the sulphuric acid treatment. The higher temperatures employed under this species temito break down the 7s batteries with of carbon monoxide and the temperature within the {range desired for the reactions discussed, the radiation and other heat losses holding the temperature at the point desired, although special artificial cooling may be used if desired, this being set forth, for example, a in my application Ser. No. 435,355,1iled January 6, 1921. The steam supplied serves to protect the products 0! oxidation from change, as well as the desired products of thermal decomposition. 'As before stated, the catalyst is preferably nonvolatile at the temperature named. 1

Example 2.-The catalytic apparatus was generally of the one-screen type described in previous of my patents, the screen catalyst being of vanadium' pentoxide mounted on asbestos, (85% oxide and 15%.asbestos). The free volume of the reacting chamber was such that the gases and'vapo'rs of the feed-were in contact with the catalyst for about two seconds.- Heat was continuously applied in regulatedv amount to maintain the temperature. The material oxidized consisted of commercial Rennsylvania wax distillate with.a specific gravity of .852 at 60 F. A run of five hours was made with the temperature of the catalytic zone about 535 0. Air feed, 18 liters per minute oil feed, 1.17 liters per hour and water feed, about 260 cc. per. hour.

At the high-temperature used, thermal decomposition of the oxidized products resulted in a 40 considerable amount of gaseous substances not recovered. Theactualoil oxidation mixture condensed and recovered amounted to 56% by'volume of the oil fed. The specific gravity of the oil oxidationproduct was .873 at 60 F. Its general composition was indicated from the follow- 'ing tests: concentrated sulphuric acid gave a 57% oxidation product in containing a higher percentage of unsaturateds. I

Aportion of the oxidized oil was vacuum-distilled to a residue of 10% .by volume,'and the condensate sulphated-sulphonated in the usual way,

as set forth in my Patent No. 1,753,516, and sulphate-sulphonate soaps then prepared. This resulted in the recovery of 14.2% of sodium soaps from theoil sulphated, an increaseof 50% over a 60 lower temperature (48C.) oxidation. These soaps thus produced showed good stability in hard water.

This second species or method shows another way or increasing the sulphated material from hydrocarbon mixtures 1 By operating my vapor phase partial oxidation process at these higher temperatures, I increase the cracking reaction and, in eflect, obtain partial'oxidation andthermal decomposition in one 7 physical step,.although I believethat the therntizl decomposition usually follows the oxidation The advantages of my invention resiQt from the process'which forms detergents oifbetterquality, 15

aoaasoi the reaction of the acid with the unsaturateds,

but the results are the same, namely, the produc- Qtion of alkyl acid salts, in this case, sulphates.

Hence, in obtaining detergents, I procure a larger 1 percentage by increasing the unsaturateds. Still moreimportant, I obtain a larger percentage of detergents within the desirable range, since as above shown. the cracking of the oxidized mate- 3 rial givesa larger percentage of longer chains having a larger number of carbon atoms. Hence, there is a peculiar and specific coaction between increasing the unsaturateds in a partial oxidation product and the step of sulphating-sulphonating to, obtaindetergents, both as regards quantity and quality of the product thus obtained.

While I do not wish to be limited to my theory that, when the higher temperature is used in my partial oxidation process, the increasedcracking is that of already oxidized material, nevertheless, for the purposes of my broader claims, I shall use theterms "cracking and "partial oxidation product in this sense to cover both species herein described. a

i I consider myself-the first to discover the special advantages of increasing the unsaturateds in such a product and then forming alkyl acid sulphates therefrom.

I claim:

1. In the manufacture oi alkylacid salts, the

steps consisting of partially oxidizing liquid hydrocarbon, cracking the partially oxidized material, and then treating the same with a polybasic mineral acid to obtain alkyl acid salts.

2. In the manufacture of alkyl acid salts, the

unsaturates in the product mixture from partial oxidation of liquid hydrocarbons by free oxygen by cracking the same and then sulphating-sulphonating the product.

3. In the manufacture of alkyl acid salts, the steps consisting of increasing the percentage of unsaturates in the product mixture from partial oxidation of liquid hydrocarbons by free oxygen 1 by cracking the same, fractioning the product,

and treating a heavier fraction with a polybasic mineral acid to produce alkyl acid salts.

4. In the manufacture of alkyl acid salts, the steps consisting of increasing the percentage of unsaturates in the product mixture from partial oxidation of liquid hydrocarbons by free oxygen by cracking the same, fractioning the product, and sulphating-sulphonating a heavier fraction.

5. As a new article of manufacture, a mixture of alkyl acid salts obtained by treating the cracked partial oxidation product from partial oxidation of a liquid hydrocarbon with free oxygen with a polybasic mineral acid to obtain alkyl of alkyl acid salts obtained by treating a heavier fraction of a cracked partial oxidation product from partial oxidation of a liquid hydrocarbon with free oxygen with a polybasic mineral acid to obtain alkyl acid salts. I

steps consistingof increasing the percentage of 7. In the manufacture of alkyl acid salts, the

steps consisting of increasing the percentage of unsaturateds in a partial oxidation mixture by cracking the same, fractioning the product into fractions of different boiling ranges, but containing like bodies and treating one of said fractions with a polybaslc mineral acid.

JOSEPH HIDY JAMES. 

